WO2015005153A1 - ビニルアセタール系重合体 - Google Patents

ビニルアセタール系重合体 Download PDF

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WO2015005153A1
WO2015005153A1 PCT/JP2014/067279 JP2014067279W WO2015005153A1 WO 2015005153 A1 WO2015005153 A1 WO 2015005153A1 JP 2014067279 W JP2014067279 W JP 2014067279W WO 2015005153 A1 WO2015005153 A1 WO 2015005153A1
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vinyl
vinyl alcohol
acetal polymer
alcohol copolymer
polyfunctional monomer
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PCT/JP2014/067279
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English (en)
French (fr)
Japanese (ja)
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徳地　一記
熊木　洋介
達也 谷田
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株式会社クラレ
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Priority to JP2015526264A priority Critical patent/JP6442405B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/38—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an acetal or ketal radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/28—Condensation with aldehydes or ketones

Definitions

  • the present invention relates to a vinyl acetal polymer obtained by acetalizing a water-soluble vinyl alcohol copolymer obtained by saponifying a copolymer of vinyl acetate and a polyfunctional monomer.
  • a method of reducing the degree of polymerization of the vinyl alcohol copolymer as a raw material is generally used as a method of reducing the viscosity of the vinyl acetal polymer. Used for.
  • the degree of polymerization of the vinyl alcohol copolymer is lowered, the mechanical properties such as strength of the vinyl acetal polymer are lowered. For this reason, applications where such a low-polymerization degree vinyl acetal polymer can be used are limited to some applications.
  • a double bond is introduced into the molecule of the vinyl acetal polymer to perform crosslinking. Proposed. For example, by reacting a compound having an ethylenic double bond with a functional group capable of reacting with a hydroxyl group such as an isocyanate group or a glycidyl group in the molecule with the residual hydroxyl group of polyvinyl acetal, the molecular weight of the vinyl acetal polymer is increased. It is disclosed that a double bond is introduced into and crosslinked with each other (see, for example, Patent Documents 1 and 2).
  • Patent Document 2 describes that, by reacting a predetermined compound having an epoxy group and an ethylenic double bond in the molecule with polyvinyl acetal, the viscosity can be lowered with almost no change in the molecular weight of polyvinyl acetal. Has been.
  • a compound having a functional group such as an aldehyde group or an acetal group and an ethylenic double bond in the molecule is used as another method for introducing a double bond into a molecule of a vinyl acetal polymer and crosslinking it.
  • a compound having a functional group such as an aldehyde group or an acetal group and an ethylenic double bond in the molecule is used as another method for introducing a double bond into a molecule of a vinyl acetal polymer and crosslinking it.
  • the above-mentioned problem is a vinyl acetal polymer obtained by acetalizing a vinyl alcohol copolymer obtained by saponifying a copolymer of vinyl acetate and a polyfunctional monomer; , Which contains two or more ethylenic double bonds in the molecule, the vinyl alcohol copolymer contains an ethylenic double bond in the side chain, and the ethylenic group with respect to the total of vinyl alcohol units and vinyl acetate units
  • This is solved by providing a vinyl acetal polymer having a double bond molar ratio (d) of 0.05 / 100 to 2/100 and a degree of acetalization of 45 to 80 mol%.
  • the side chain preferably contains a vinyl ether group. It is also preferred that the side chain contains an allyl group.
  • a vinyl acetal polymer having an ethylenic double bond introduced in the side chain can be provided.
  • the vinyl acetal polymer of the present invention is excellent in solubility in an alcohol solvent and the like, and has low solution viscosity and melt viscosity, and is excellent in handleability. Further, the viscosity can be lowered while maintaining the mechanical properties such as strength. Accordingly, the vinyl acetal polymer is suitable for various uses such as an interlayer film composition for laminated glass, a ceramic slurry composition, an ink composition / coating composition, an adhesive composition, and a heat-developable photosensitive material composition. Used for.
  • Example 1 is a 1 H-NMR spectrum of polyvinyl acetate obtained in Example 1.
  • 1 is a 1 H-NMR spectrum of a vinyl alcohol copolymer obtained in Example 1.
  • the present invention relates to a vinyl acetal polymer obtained by acetalizing a vinyl alcohol copolymer obtained by saponifying a copolymer of vinyl acetate and a polyfunctional monomer.
  • the vinyl alcohol copolymer is preferably water-soluble.
  • the vinyl acetal polymer of the present invention is preferably obtained by acetalizing a water-soluble vinyl alcohol copolymer while containing an ethylenic double bond in its side chain.
  • the polyfunctional monomer used in the present invention contains two or more ethylenic double bonds in the molecule and is not particularly limited. However, it is preferable that an excessive amount of double bonds can be introduced without inhibiting the water solubility of the vinyl alcohol copolymer by the excessive crosslinking reaction. It is necessary to select a polyfunctional monomer with appropriate reactivity in consideration of various factors such as blending ratio of polyfunctional monomer to vinyl acetate, polymerization temperature, monomer concentration, polymerization rate, polymerization degree, etc. There is. From the viewpoint of suppressing an excessive crosslinking reaction, the number of ethylenic double bonds contained in the polyfunctional monomer is preferably two.
  • the polyfunctional monomers exemplified below can be used alone or in combination of two or more.
  • ethanediol divinyl ether propanediol divinyl ether, butanediol divinyl ether (for example, 1,4-butanediol divinyl ether), ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether
  • monomers containing vinyl ether groups such as divinyl ether compounds such as polyethylene glycol divinyl ether, propylene glycol divinyl ether, polypropylene glycol divinyl ether, and tetraethylene glycol divinyl ether.
  • Monomers containing vinyl ether groups can easily control the degree of polymerization of vinyl alcohol copolymer and the content of double bonds. More preferably used.
  • a monomer containing an allyl group is also suitable.
  • Monomers containing an allyl group include diene compounds such as pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene (for example, 1,9-decadiene), glycerin diallyl ether, diethylene glycol diallyl ether, ethylene glycol diallyl ether, triglyceride.
  • Diallyl ether compounds such as ethylene glycol diallyl ether, polyethylene glycol diallyl ether, trimethylolpropane diallyl ether, pentaerythritol diallyl ether, triallyl ether compounds such as glycerol triallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, Tetraallyl ether compounds such as pentaerythritol tetraallyl ether Monomers containing allyl ether groups; monomers containing allyl ester groups such as diallyl carboxylates such as diallyl phthalate, diallyl maleate, diallyl itaconate, diallyl terephthalate, diallyl adipate; diallylamine, diallyl A monomer containing an allylamino group such as diallylamine compounds such as methylamine and triallylamine; a monomer containing an allylammonium group such as dial
  • Monomers containing allyl ether groups can easily control the degree of polymerization of the vinyl alcohol copolymer and the content of double bonds. Yes, more preferably used.
  • Monomers having (meth) acrylic acid monomers having (meth) acrylamides such as N, N′-methylenebis (meth) acrylamide and N, N′-ethylenebis (meth) acrylamide, divinylbenzene, trivinylbenzene And so on.
  • the vinyl alcohol copolymer used in the present invention is produced by copolymerizing vinyl acetate and a polyfunctional monomer to obtain a vinyl ester copolymer, and then saponifying the vinyl ester copolymer. Is done. According to this production method, a vinyl alcohol copolymer in which a component derived from a polyfunctional monomer is uniformly distributed in a molecular chain can be obtained.
  • molar ratio (p) it is preferable to copolymerize the polyfunctional monomer to vinyl acetate in a molar ratio (p) of 0.1 / 100 to 5/100. If the molar ratio (p) is less than 0.1 / 100, it may be difficult to introduce an ethylenic double bond into the side chain.
  • the molar ratio (p) is more preferably 0.15 / 100 or more, and further preferably 0.2 / 100 or more. On the other hand, when the molar ratio (p) exceeds 5/100, it may be difficult to control the degree of polymerization of the vinyl ester copolymer. Further, the vinyl alcohol copolymer obtained by saponifying the vinyl ester copolymer may not be dissolved in water.
  • the molar ratio (p) is more preferably 3/100 or less, and even more preferably 2/100 or less.
  • any polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be employed.
  • the copolymerization can be carried out without solvent or in the presence of an alcohol solvent.
  • a solvent-free bulk polymerization method and a solution polymerization method using an alcohol solvent are preferably employed.
  • the alcohol solvent is not particularly limited, and for example, methanol, ethanol, propanol and the like can be used alone or in admixture of two or more.
  • the copolymerization method is not particularly limited, and any of batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization may be used.
  • the temperature at the time of copolymerizing vinyl acetate and a polyfunctional monomer is not particularly limited.
  • the copolymerization temperature is preferably 0 to 200 ° C, more preferably 30 to 140 ° C. When the copolymerization temperature is lower than 0 ° C., a sufficient polymerization rate may not be obtained. When the copolymerization temperature is higher than 200 ° C., there is a concern about the decomposition of the vinyl acetate or polyfunctional monomer used.
  • the method for controlling the copolymerization temperature is not particularly limited.
  • Examples of the method for controlling the copolymerization temperature include a method of balancing the heat generated by the polymerization and the heat radiation from the surface of the polymerization vessel by controlling the polymerization rate.
  • the method of controlling by the external jacket using a suitable heat medium is also mentioned. The latter method is preferable from the viewpoint of safety.
  • a polymerization initiator used when copolymerizing vinyl acetate and a polyfunctional monomer is a known initiator (for example, an azo initiator, a peroxide initiator, a redox system) depending on the polymerization method. Initiator etc.) may be selected.
  • the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile).
  • peroxide-based initiator examples include percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl peroxyneodecanate, ⁇ -Perester compounds such as cumylperoxyneodecanate and t-butylperoxydecanate; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate and the like.
  • These initiators may be combined with potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like as an initiator.
  • the redox initiator examples include an initiator in which the above peroxide is combined with a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, or longalite.
  • a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, or longalite.
  • an antioxidant such as tartaric acid may be added to the polymerization system in an amount of about 1 to 100 ppm based on vinyl acetate.
  • the copolymerization of vinyl acetate and a polyfunctional monomer is carried out in the presence of a chain transfer agent within the range not impairing the gist of the present invention, for the purpose of adjusting the degree of polymerization of the resulting copolymer.
  • a chain transfer agent within the range not impairing the gist of the present invention, for the purpose of adjusting the degree of polymerization of the resulting copolymer.
  • the chain transfer agent include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; halogenated hydrocarbons such as trichloroethylene and perchloroethylene. It is done. Of these, aldehydes and ketones are preferably used.
  • the addition amount of the chain transfer agent may be determined according to the chain transfer constant of the chain transfer agent to be added and the degree of polymerization of the target
  • the polymerization rate of vinyl acetate is preferably 20 to 90%. If the polymerization rate of vinyl acetate is less than 20%, the amount of vinyl ester copolymer that can be produced per unit time may decrease, resulting in a decrease in production efficiency, and the cost for recovering vinyl acetate. May increase. From the viewpoint of production efficiency and cost, the polymerization rate of vinyl acetate is more preferably 30% or more, and further preferably 40% or more. On the other hand, when the polymerization rate of vinyl acetate exceeds 90%, the crosslinking reaction proceeds excessively, and the water solubility of the resulting vinyl alcohol copolymer may be lowered.
  • the polymerization rate of vinyl acetate is more preferably 80% or less, and further preferably 70% or less.
  • the measurement of a polymerization rate calculates the solid content of a polymer by vacuum-drying the obtained polymer solution at 120 degreeC for 2 hours.
  • the saponification method of the vinyl ester copolymer obtained by copolymerizing vinyl acetate and a polyfunctional monomer is not particularly limited, and a known saponification method can be adopted.
  • a basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide or an acidic catalyst such as p-toluenesulfonic acid
  • the solvent that can be used in this reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone methyl ethyl ketone: aromatic hydrocarbons such as benzene and toluene. . These solvents can be used alone or in combination of two or more.
  • saponification using methanol or a methanol / methyl acetate mixed solution as a solvent and sodium hydroxide as a catalyst is convenient and preferable.
  • the saponification degree of the vinyl alcohol copolymer used in the present invention is preferably 60 to 99.9 mol%. If the degree of saponification is less than 60 mol%, the vinyl alcohol copolymer may be insoluble in water.
  • the saponification degree is more preferably 65 mol% or more. On the other hand, when the degree of saponification exceeds 99.9 mol%, not only industrial production is difficult, but also the viscosity stability of the vinyl alcohol copolymer aqueous solution is deteriorated and handling may be difficult.
  • the degree of saponification is more preferably 98 mol% or less.
  • the saponification degree is a value measured by the saponification degree measuring method described in JIS K6726. At this time, units other than the vinyl alcohol unit, the vinyl acetate unit and the monomer unit containing an ethylenic double bond are a small amount even if they are contained in the vinyl alcohol copolymer. Ignore it and calculate the degree of saponification.
  • the viscosity average polymerization degree P ⁇ of the vinyl alcohol copolymer used in the present invention is preferably 100 to 8000. If the viscosity average polymerization degree P ⁇ is less than 100, industrial production may be difficult.
  • the viscosity average degree of polymerization P ⁇ is more preferably 200 or more. On the other hand, when the viscosity average polymerization degree P ⁇ exceeds 8000, not only industrial production is difficult, but also the viscosity of the aqueous vinyl alcohol copolymer solution becomes very high, which may be difficult to handle.
  • the viscosity average degree of polymerization P ⁇ is more preferably 5000 or less, and further preferably 2500 or less.
  • the viscosity average polymerization degree P ⁇ is measured according to JIS K6726. Specifically, the vinyl alcohol copolymer is saponified again to completely saponify the remaining acetate groups. The re-saponified vinyl alcohol copolymer is purified and dried, and then 1 g of the dried sample is added to 100 ml of water, dissolved by heating, and cooled to 30 ° C. The obtained aqueous solution is weighed into a viscometer, the intrinsic viscosity [ ⁇ ] (unit: L / g) in water at 30 ° C. is measured, and can be calculated from the measured intrinsic viscosity [ ⁇ ] by the following formula (1).
  • the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn obtained from the size exclusion chromatography of the vinyl alcohol copolymer used in the present invention is preferably 2 to 5, and more preferably 2 to 4. If Mw / Mn is less than 2, industrial production may be difficult. Moreover, when Mw / Mn exceeds 5, when manufacturing a vinyl acetal polymer, there exists a tendency for an acetalization reaction rate to fall.
  • the vinyl alcohol copolymer used in the present invention is preferably water-soluble and contains an ethylenic double bond in its side chain.
  • the molar ratio (d) of the ethylenic double bond to the total of vinyl alcohol units and vinyl acetate units is 0.05 / 100 to 2/100. When the molar ratio (d) is less than 0.05 / 100, mechanical properties such as strength of the obtained vinyl acetal polymer are not sufficient.
  • the molar ratio (d) is preferably 0.07 / 100 or more, and more preferably 0.1 / 100 or more.
  • the molar ratio (d) of the ethylenic double bond is preferably 1.5 / 100 or less, and more preferably 1/100 or less.
  • the vinyl alcohol copolymer used in the present invention preferably contains a vinyl ether group in its side chain. It is also preferred that the side chain contains an allyl group or an allyl ether group. Since these structures have moderately lower reactivity than the vinyl ester group contained in vinyl acetate, it is possible to increase the proportion of the monomer that only one of the double bonds reacts while suppressing the crosslinking reaction. Thereby, a water-soluble vinyl alcohol copolymer having a controlled double bond content can be obtained. Further, since the vinyl alcohol copolymer containing such a side chain has a necessary amount of double bonds and has water solubility, the vinyl acetal polymer can be economically produced on an industrial scale. It is preferable at the point which manufactures stably.
  • the amount of ethylenic double bond introduced can be determined by 1 H-NMR spectrum of vinyl alcohol copolymer in heavy water or heavy dimethyl sulfoxide solvent or vinyl ester copolymer before saponification in deuterated chloroform solvent. Measured from 1 H-NMR spectrum. The amount of ethylenic double bonds introduced is controlled by the mixing ratio of the polyfunctional monomer to the vinyl ester monomer and the polymerization rate.
  • the molar ratio of ethylenic double bonds to the total of vinyl alcohol units and vinyl acetate units from the viewpoint of introducing the necessary amount of double bonds into the vinyl alcohol copolymer while maintaining the crosslinking reaction and maintaining production efficiency.
  • the ratio (d / p) of the molar ratio (p) of the polyfunctional monomer to (d) and vinyl acetate is preferably 0.2 or more, and more preferably 0.5 or more. If the ratio (d / p) is less than 0.2, the ratio of the product in which vinyl acetate and the polyfunctional monomer are cross-linked increases, and the water solubility of the vinyl alcohol copolymer may be hindered. is there.
  • the ratio (d / p) can be increased depending on the blending ratio of polyfunctional monomer to vinyl acetate and the polymerization conditions, but the ratio (d / p) is 0.8 or less in consideration of production efficiency. Is preferred.
  • the vinyl alcohol copolymer when the vinyl alcohol copolymer is water-soluble, when an aqueous solution of 4% by mass vinyl alcohol copolymer at a temperature of 90 ° C. is prepared, the vinyl alcohol copolymer is dissolved in water. When completely dissolved.
  • the vinyl acetal polymer of the present invention can be obtained by acetalizing the vinyl alcohol copolymer obtained as described above according to a conventionally known method.
  • the degree of acetalization at this time is 45 mol% or more and 80 mol% or less.
  • the degree of acetalization of the vinyl acetal polymer is more preferably 55 mol% or more, and further preferably 60 mol%.
  • the degree of acetalization of the vinyl acetal polymer can be appropriately selected according to the solubility in the solvent used.
  • the amount of aldehyde added to the vinyl alcohol copolymer to be used, the reaction time after adding the aldehyde and the acid catalyst, and the like may be adjusted as appropriate.
  • the degree of acetalization of the vinyl acetal polymer represents the ratio of the acetalized vinyl alcohol unit to the total monomer units constituting the vinyl acetal polymer.
  • the degree of acetalization can be measured according to, for example, the method of JIS K6728 (1977).
  • a vinyl alcohol copolymer is heated and dissolved in water to prepare an aqueous solution having a concentration of 5 to 30% by mass.
  • a method of adding a predetermined amount of aldehyde after cooling to 50 ° C., cooling to ⁇ 10 ° C. to 30 ° C., and adding an acid to bring the pH of the aqueous solution to 1 or less to start acetalization (2) vinyl alcohol The aqueous copolymer is dissolved in water by heating to prepare an aqueous solution having a concentration of 5 to 30% by mass, which is cooled to 5 ° C. to 50 ° C. Examples thereof include a method of starting acetalization by cooling to ⁇ 10 ° C. to 30 ° C. and adding a predetermined amount of aldehyde.
  • aldehydes used for acetalization include formaldehyde (including paraformaldehyde), acetaldehyde (including paraacetaldehyde), propionaldehyde, butyraldehyde, isobutyraldehyde, 2-ethylbutyraldehyde, valeraldehyde, pivalaldehyde, and amylaldehyde.
  • Aliphatic aldehydes such as hexyl aldehyde, heptyl aldehyde, 2-ethylhexyl aldehyde, octyl aldehyde, nonyl aldehyde, decyl aldehyde, dodecyl aldehyde; cyclopentane aldehyde, methyl cyclopentane aldehyde, dimethyl cyclopentane aldehyde, cyclohexane aldehyde, methyl cyclohexane aldehyde, Dimethylcyclohexanealdehyde, cyclohexaneacetoaldehyde Cyclopentene aldehyde, cyclohexene aldehyde and other cyclic unsaturated aldehydes; benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldeh
  • At least one selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, hexylaldehyde, and benzaldehyde is preferable, and butyraldehyde is particularly preferable.
  • an aldehyde used for acetalization an aldehyde having a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group or the like as a functional group may be used as long as the effects of the present invention are not impaired.
  • the acid used for the acetalization is not particularly limited, and examples thereof include acetic acid, paratoluenesulfonic acid, nitric acid, sulfuric acid, hydrochloric acid and the like. Among these, hydrochloric acid, sulfuric acid, and nitric acid are preferable, hydrochloric acid and nitric acid are more preferable, and two or more of these may be used in combination.
  • the time required for the acetalization reaction is usually about 1 to 10 hours, and the reaction is preferably carried out with stirring. In addition, when the acetal is performed under the above-described temperature conditions, the reaction may be continued at a high temperature of about 50 ° C. to 80 ° C. if the degree of acetalization of the vinyl acetal polymer does not increase.
  • the granular reaction product obtained after the acetalization is filtered off, washed thoroughly with water, added with a neutralizing agent such as alkali, washed and dried to obtain the desired vinyl acetal polymer.
  • a neutralizing agent such as alkali
  • alkali compound used as a neutralizing agent include sodium hydroxide and potassium hydroxide.
  • the vinyl acetal polymer of the present invention is an acetalized product of a copolymer of a polyfunctional compound having two or more ethylenic double bonds in the molecule and vinyl alcohol, and has an ethylenic double bond in the side chain. Is 0.05 to 2 mol% relative to the vinyl alcohol unit and its derivative, and the degree of acetalization is 45 to 80 mol%.
  • the derivative unit of a vinyl alcohol unit means an acetal unit obtained by acetalizing a vinyl acetate unit or a vinyl alcohol unit remaining without being saponified in the production process of a vinyl alcohol copolymer.
  • the amount of the ethylenic double bond is preferably 0.07 mol% or more, and more preferably 0.1 mol% or more.
  • the amount of the ethylenic double bond is less than 0.05 mol%, sufficient mechanical properties such as strength cannot be obtained. Moreover, it is preferable that it is 1.5 mol% or less, and it is more preferable that it is 1 mol% or less.
  • the amount of the ethylenic double bond exceeds 2 mol%, the vinyl alcohol copolymer used for the production of the vinyl acetal polymer is likely to be insoluble in water and difficult to produce.
  • the amount of the ethylenic double bond is determined by the 1 H-NMR spectrum of the vinyl acetal polymer in the heavy dimethyl sulfoxide solvent, the heavy alcohol or heavy dimethyl sulfoxide solvent of the vinyl alcohol copolymer before the acetalization. It is measured from a 1 H-NMR spectrum or a 1 H-NMR spectrum in a deuterated chloroform solvent of a vinyl ester copolymer before saponification. Basically, the amounts of ethylenic double bonds measured at each stage of vinyl acetal polymer, vinyl alcohol polymer, and vinyl ester polymer are the same.
  • the vinyl acetal polymer of the present invention produced in this way is excellent in solubility in alcohol solvents and the like, and has a low solution viscosity and excellent handleability. Therefore, the vinyl acetal polymer of the present invention is used for various types of interlayer film compositions for laminated glass, ceramic slurry compositions, ink compositions / coating compositions, adhesive compositions, heat-developable photosensitive material compositions, and the like. It is suitably used for applications.
  • parts and% represent parts by mass and mass%, respectively.
  • the viscosity average polymerization degree P ⁇ of the vinyl alcohol copolymer was measured according to JIS K6726. Specifically, the remaining alcohol group was completely saponified by saponifying the vinyl alcohol copolymer again. The re-saponified vinyl alcohol copolymer was purified and dried, and then 1 g of the dried sample was added to 100 ml of water, dissolved by heating, and cooled to 30 ° C. The obtained aqueous solution was weighed in a viscometer, and the intrinsic viscosity [ ⁇ ] (unit: L / g) in water at 30 ° C. was measured. The viscosity average degree of polymerization P ⁇ was calculated from the measured intrinsic viscosity [ ⁇ ] by the following formula (2).
  • the vinyl alcohol copolymer was measured by the method for measuring the degree of saponification described in JIS K6726.
  • Example 1 Synthesis of vinyl alcohol copolymer PVA-1 having an ethylenic double bond in the side chain
  • a 6-liter reaction vessel equipped with a stirrer, nitrogen inlet, additive inlet and initiator inlet is charged with 1200 g of vinyl acetate, 1800 g of methanol, and 19.8 g of 1,4-butanediol divinyl ether as a polyfunctional monomer. After raising the temperature to 60 ° C., the system was purged with nitrogen by carrying out nitrogen bubbling for 30 minutes. The temperature in the reaction vessel was adjusted to 60 ° C., and 2.5 g of 2,2′-azobis (isobutyronitrile) was added to initiate polymerization.
  • 2,2′-azobis isobutyronitrile
  • the polymerization temperature was maintained at 60 ° C. during the polymerization. After 3 hours, when the polymerization rate of vinyl acetate reached 58%, the polymerization was terminated by cooling. Next, unreacted vinyl acetate was removed under reduced pressure to obtain a methanol solution of polyvinyl acetate (hereinafter sometimes abbreviated as PVAc).
  • PVAc polyvinyl acetate
  • the PVAc thus obtained was subjected to reprecipitation purification using acetone as a good solvent and hexane as a poor solvent five times and dried by vacuum drying. Thereafter, the obtained PVAc was dissolved in deuterated chloroform, and 1 H-NMR measurement was performed. The measurement results are shown in FIG. From the spectrum of FIG.
  • the amount of ethylenic double bonds introduced relative to the total of vinyl alcohol units and vinyl acetate units was calculated to be 0.5 mol%.
  • concentration of the solution was adjusted to 30% by mass, and the alkali molar ratio (number of moles of NaOH / number of moles of vinyl ester units in PVAc) was 0.006.
  • NaOH methanol solution (10% concentration) was added so as to be saponified.
  • the obtained vinyl alcohol copolymer was washed with methanol.
  • a vinyl alcohol copolymer having a viscosity average polymerization degree of 1070 and a saponification degree of 79.6 mol% was obtained.
  • the obtained vinyl alcohol copolymer was dissolved in water at 90 ° C. to prepare a 4% by mass aqueous solution, it was completely dissolved.
  • the obtained vinyl alcohol copolymer was dissolved in deuterated dimethyl sulfoxide, and 1 H-NMR measurement was performed. The measurement results are shown in FIG. From the spectrum of FIG. 2 obtained, the amount of ethylenic double bonds introduced relative to the total of vinyl alcohol units and vinyl acetate units was calculated to be 0.5 mol%.
  • VAP-1 vinyl acetal polymer
  • the degree of acetalization of the obtained vinyl acetal polymer VAP-1 was measured and found to be 70.2 mol%. Further, the viscosity of a 5 mass% ethanol / water (95 mass% / 5 mass%) solution of the obtained vinyl acetal polymer was a value shown in Table 2. Further, a film having a thickness of 100 ⁇ m was prepared by a cast film forming method using the above 5% by mass ethanol / water (95% by mass / 5% by mass) solution, and the tensile strength of this film was measured. The results are shown in Table 2.
  • Examples 2 to 7 Vinyl alcohol copolymers PVA-2 to PVA-7 in the same manner as in Example 1 except that the types and amounts of polyfunctional monomers used and the amounts of vinyl acetate and methanol are as shown in Table 1. Got. Tables 1 and 2 show the evaluation results of the vinyl alcohol copolymers PVA-2 to PVA-7. Also, vinyl acetal polymers VAP-2 to VAP-7 were obtained in the same manner as in Example 1 except that PVA shown in Table 2 was used instead of PVA-1. Table 2 shows the evaluation results of the vinyl acetal polymers VAP-2 to VAP-7.
  • the amount of ethylenic double bonds relative to the total amount of vinyl alcohol units of VAP-6 and derivatives thereof (vinyl acetate units and acetal units) was measured by 1 H-NMR in the same manner as the vinyl alcohol polymer. 0.2 mol%, which was no difference from the amount of ethylenic double bonds in the starting vinyl alcohol polymer.
  • Example 8 A vinyl acetal polymer VAP-8 was obtained in the same manner as in Example 7 except that the amount of butyraldehyde added was reduced. The evaluation results of the vinyl acetal polymer VAP-8 are shown in Table 2.
  • Example 9 A vinyl acetal polymer VAP-9 was obtained in the same manner as in Example 7 except that the amount of butyraldehyde added was increased. Table 2 shows the evaluation results of the vinyl acetal polymer VAP-9.
  • Example 10 A vinyl alcohol copolymer PVA-8 was obtained in the same manner as in Example 1 except that the type and amount of the polyfunctional monomer used were as shown in Table 1.
  • a vinyl acetal polymer VAP-10 was obtained in the same manner as in Example 1 except that the vinyl alcohol copolymer PVA-8 was used instead of PVA-1.
  • Table 2 shows the evaluation results of the vinyl acetal polymer VAP-10.
  • Vinyl alcohol copolymers PVA-C1 and PVA-C2 were prepared in the same manner as in Example 1 except that no polyfunctional monomer was used and the amounts of vinyl acetate and methanol were changed as shown in Table 1. Obtained.
  • Tables 1 and 2 show the evaluation results of the vinyl alcohol copolymers PVA-C1 and PVA-C2.
  • Vinyl acetal polymers VAP-C1 and VAP-C2 were obtained in the same manner as in Example 1 except that vinyl alcohol copolymers PVA-C1 and PVA-C2 were used instead of PVA-1.
  • Table 2 shows the evaluation results of the vinyl acetal polymers VAP-C1 and VAP-C2.
  • a vinyl alcohol copolymer PVA-C3 was obtained in the same manner as in Example 1 except that the amount of the polyfunctional monomer charged was changed as shown in Table 1.
  • Tables 1 and 2 show the evaluation results of the vinyl alcohol copolymer PVA-C3.
  • a vinyl acetal polymer VAP-C3 was obtained in the same manner as in Example 1 except that the vinyl alcohol copolymer PVA-C3 was used instead of PVA-1.
  • Table 2 shows the evaluation results of the vinyl acetal polymer VAP-C3.
  • Example 4 A vinyl alcohol-based copolymer is used in the same manner as in Example 1 except that acetaldehyde is used in place of the polyfunctional monomer in the amounts shown in Table 1, and that the amounts of vinyl acetate and methanol are shown in Table 1.
  • the combined PVA-C4 was obtained.
  • Tables 1 and 2 show the evaluation results of the vinyl alcohol copolymer PVA-C4.
  • a vinyl acetal polymer VAP-C4 was obtained in the same manner as in Example 1 except that the vinyl alcohol copolymer PVA-C4 was used instead of PVA-1.
  • Table 2 shows the evaluation results of the vinyl acetal polymer VAP-C4.

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EP3208286A4 (en) * 2014-10-17 2018-05-16 Kuraray Co., Ltd. Vinyl alcohol polymer and use thereof

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